Self-generated hierarchically porous titania with high surface area: photocatalytic activity enhancement by macrochannel structure

Various hierarchical porous titania with high surface area over 600 m(2)/g have been synthesized via a spontaneous self-formation process from titanium alkoxides by a water adjusting approach using acetonitrile as reaction medium. The reactivity of metal alkoxides and the water content in acetonitrile medium on the resultant structure have been investigated. The porosities of the products were characterized by SEM, TEM and N(2) adsorption-desorption measurements. The observation on the evolution of porous structure with increasing water content in reaction system is essential for a better understanding of hierarchical porous structure formation over different length scales by this self-formation process. The creation of macro/micropores in photocatalytic titania materials has been found to enhance the photocatalytic activity due to both the action of macrochannels as light harvester and the easy diffusion effect of organic molecules. The present work shows clearly that hierarchically porous titania with the presence of macroporous structure and high surface area can be very efficient photocatalysts, suggesting their potential applications in water treatment as decontamination materials.     

Tailoring the porous hierarchy and the tetrahedral aluminum content by using carboxylate ligands: hierarchically structured macro-mesoporous aluminosilicates from a single molecular source

A novel yet facile synthesis pathway has been developed for the design of hierarchically structured macro-mesoporous aluminosilicates with high aluminum content at tetrahedral sites using a single molecular bifunctional alkoxide (sec-BuO)(2)-Al-O-Si(OEt)(3) precursor. The use of carboxylate ligands and a highly alkaline media slow down the polymerization rate of the aluminum alkoxide functionality, thus permitting the preservation of the intrinsic Al-O-Si linkage. The hierarchically structured porous aluminosilicate materials present an unprecedented low Si/Al ratio close to 1. Heat treatment applied to the synthesized material seems to favor the incorporation of aluminum into tetrahedral position (intraframework aluminum species). The macro-mesoporosity was spontaneously generated, without the use of any external templating agent, by the hydrodynamic flow of the solvents released during the rapid hydrolysis and condensation processes of this double alkoxide. This method results in materials with an open array of interconnected macrochannels. The synthesized aluminosilicate materials with tailorable macro-mesoporous hierarchy and very high Al content at tetrahedral position hold huge promise in various applications as catalysts, catalysts supports, or adsorbents.     

Hierarchical porous materials made by drying complex suspensions

Porous structures containing pores at different length scales are often encountered in nature and are important in many applications. While several processing routes have been demonstrated to create such hierarchical porous materials, most methods either require chemical gelation reactions or do not allow for the desired control of pore sizes over multiple length scales. We describe a versatile and simple approach to produce tailor-made hierarchical porous materials that relies solely on the process of drying. Our results show that simple drying of a complex suspension can lead to the self-assembly of droplets, colloidal particles and molecular species into unique 3D hierarchical porous structures. Using a microfluidic device to produce monodisperse templating droplets of tunable size, we prepared materials with up to three levels of hierarchy exhibiting monodisperse pores ranging from 10 nm to 800 μm. While the size of macropores obtained after drying is determined by the size of initial droplets, the interconnectivity between macropores is strongly affected by the type of droplet stabilizer (surfactants or particles). This simple route can be used to prepare porous materials of many chemical compositions and has great potential for creating artificial porous structures that capture some of the exquisite hierarchical features of porous biological materials.     

Novel architectures in porous materials based on clays

Modification of layered clays in view to develop porous materials, mainly for catalytic applications, has been afforded in the past via intercalation reaction of aluminum and other polyoxycations or through generation of mesoporous silica between the layers of the silicate. In this paper it is introduced examples of an alternative route for the preparation of porous nanoarchitectures based on the sol–gel method that profits from the swelling ability of organoclays in organic solvents to incorporate silicon and/or other metal (e.g., Ti, Al,…) alkoxides in the interlayer region of the silicates where they are hydrolyzed in a controlled manner. Their further polycondensation originates the formation of an oxide matrix and after a thermal treatment is possible the consolidation of oxide nanoparticles between delaminated smectites and vermiculites. It is also showed how this colloidal route can be applied to the generation of oxide nanoparticles bonded to the external surface of fibrous clays, such as sepiolite. Finally, it is also summarized with various examples the potential interest of the resulting porous clay nanoarchitecture materials in applications as acid catalysts, photocatalysts or nanofillers in polymer–clay nanocomposites.     

Hierarchically imprinted porous films for rapid and selective detection of explosives

On the basis of the combination of colloidal and mesophase templating, as well as molecular imprinting, a general and effective approach for the preparation of hierarchically structured trimodal porous silica films was developed. With this new methodology, controlled formation of well-defined pore structures not only on macro- and mesoscale but also on microscale can be achieved, affording a new class of hierarchical porous materials with molecular recognition capability. As a demonstration, TNT was chosen as template molecule and hierarchically imprinted porous films were successfully fabricated, which show excellent sensing properties in terms of sensitivity, selectivity, stability, and regeneracy. The pore system reported here combines the multiple benefits arising from all length scales of pore size and simultaneously possesses a series of distinct properties such as high pore volume, large surface area, molecular selectivity, and rapid mass transport. Therefore, our described strategy and the resulting pore systems should hold great promise for various applications not only in chemical sensors, but also in catalysis, separation, adsorption, or electrode materials.     

溶致液晶及其在纳米结构材料合成中的应用*

有序纳米结构材料是一类具有广泛应用前景的新材料,在分离、催化、传感器等领域的应用潜力巨大。近年来,利用溶致液晶模板合成纳米结构颗粒和薄膜材料的研究取得了一系列重要进展,包括新纳米结构金属和半导体材料的合成、由过渡金属水合物与表面活性剂构建的新液晶体系、溶致液晶与其它模板结合制备具有多级孔结构的新材料、影响液晶体系及纳米结构材料有序性与稳定性的关键因素、以及纳米结构形成机理等方面的内容。本文就上述几个方面的近期研究成果进行了总结与综述,并展望了利用溶致液晶模板合成纳米结构材料需要进一步深入开展的内容,有助于化学、化学工程和材料科学等领域的相关研究工作。     

Synthesis and Characterization of Fluoro- and Chloro- bimetallic Alkoxides as Precursors for Luminescent Metal Oxide Materials via Sol-Gel Technique

Heterobimetallic alkoxides are broadly recognized as versatile precursors for luminescence materials, and efforts are being made to develop novel routes by applying the concept of geometrical molecular design, for their synthesis and to design a single source precursor suited to photoluminescent materials. Novel and new series of bimetallic alkoxides has been prepared by metathesis route. They exhibit a lower sensitivity towards hydrolysis and so they are easier to handle as compared to other alkoxides. All the compounds were characterized by elemental analysis, FT-IR and multinuclear NMR spectroscopies. FT-IR revealed that the molecular structure of these metal alkoxides was retained to a large extent in 4 ： 1 halogenated alcohol-benzene solution. The heteronuclear NMR spectroscopy provided useful information about chemical shifts for better understanding the likely structure based on interactions with their coordinate metals. The mass spectra show similar types of fragmentation pattern. SEM-EDS analyses showed consistency with the formulation. XRD patterns show an enhanced homogeneity at high temperature. TGA measurements show that thermal decomposition occured in steps that depended entirely on the chemical compositions and the synthesis routes. SEM observation reveals that the morphology and particle size strongly depend on synthesis routes for their precursors.     

Molecular Design of Novel Heterometallic Alkoxides as Precursors

In view of the advantages of employing heterometallic alkoxides as precursors for ceramic materials by the sol-gel process, efforts are being made to develop novel routes for their synthesis and to design single source precursors suited to the final targeted material. Three such new pathways are briefly presented in this paper: (i) varying the ratio of constituent metals; (ii) dissolution of metal chlorides in alkoxides of tetravalent metals; and (iii) reactions of acidic protons of metal glycolate derivatives with alkoxides of another metal yielding derivatives containing other alkoxometallates in cationic form.     

Thermally stable macroporous zirconium phosphates with supermicroporous walls: a self-formation phenomenon of hierarchy

A self-formation phenomenon leading to the hierarchically thermally stable macroporous zirconium phosphates with amorphous supermicroporous walls from the precursors of zirconium propoxide and orthophosphoric acid solution was observed.     

High Internal Phase Emulsion Templating – A Path To Hierarchically Porous Functional Polymers

Recently, a series of new monomers and polymerization mechanisms has been applied to the templating of high internal phase emulsions (HIPEs) providing a route to hierarchically porous materials with a range of functionalities and applications. The high degree of control over the pore size is another attractive feature of these materials. Usually, the continuous phase contains monomers, the droplet phase is used to template the large, primary pores, which are interconnected by secondary pores. The addition of nonpolymerizable components to the continuous phase can result in phase separation during polymerization and tertiary pores. Applications include polymer supports for catalysis and synthesis, separation and filtration, cell culture media, enzyme supports, and structural and isolation applications.     

Metal alkoxides and β-diketonates as precursors for oxide and non-oxide thin films

Single-components or multicomponent oxide thin films are of interest for electronic and opto-electronic devices, optical applications, catalysis, corrosion protection etc. Their preparation by chemical routes is based on the hydrolytic (sol-gel process) or pyrolytic (MOCVD) conversion of precursors. Derivatives having M? O bonds, namely metal alkoxides, carboxylates or β-diketonates, are the most common sources of metal oxides. The properties of alkoxides are appropriate for sol-gel as well as MOCVD applications, whilst the limited hydrolytic susceptibility but good volatility of β-diketonates is most convenient for MOCVD purposes. The low temperature and flexibility of sol-gel routes, and the presence of residual OH groups in the final films, are favorable for the encapsulation of organic or organometallic derivatives, the anchoring of enzymes and in general for the development of functional and composite coatings. The facile formation of heterometallic alkoxides is also attractive for the development of coatings based on multimetallic formulations. MOCVD is favorable for the buildup of heterostructures and epitaxial layers. Although metal alkoxides and β-diketonates are usually oxide precursors, nitride or sulfide films can be obtained by reacting with the appropriate reagents. Fluorinated ligands enhance volatility but often result in the formation of metal fluorides.     

Hierarchically Porous Organic Materials Derived From Copolymers: Preparation and Electrochemical Applications

Abstract

Compared to conventional porous materials with a uniform pore size distribution, hierarchical ones containing interconnected macro-, meso-, and micropores have greatly enhanced material performance due to the increased specific surface area and mass transfer. Copolymer is a good candidate used for construction of such hierarchically porous structures, resulting from its tunable segment composition, unique phase separation, and self-assembly, etc. Hierarchically porous materials derived from copolymers can be served as a versatile support for many reactive molecules. Furthermore, hierarchically porous carbon materials (HPCMs) can also be prepared by carbonization of copolymers, one segment of which is converted to carbon while the other segment is responsible for the pore formation after its removal by pyrolysis. The obtained hierarchically porous copolymers or carbon materials have promising electrochemical applications especially in energy conversion and storage. In the present review, recent advances in preparation of hierarchically porous materials (HPMs) derived from copolymers are reviewed, and their electrochemical applications in supercapacitors, lithium-ion batteries, fuel cells, electrochemical biosensors, and electrocatalysis are also introduced. The rational design and control for the hierarchically porous microstructures are described deeply from the molecular level. Also, the relationship between the micro-structure and the electrochemical performance is revealed. This review can provide us a better understanding of both theory and experiment for the preparation of hierarchically porous organic materials and their electrochemical applications.     

衍生多孔碳材料在固相微萃取中的应用研究进展

固相微萃取是一种集采样、萃取、富集和进样于一体的样品前处理技术,其萃取效果与涂层材料密切相关。多孔碳材料具有比表面积大、多孔结构可控、活性位点多和化学稳定性好等优点,广泛应用于电池、超级电容器、催化、吸附和分离等领域,也是一种热门的用作固相微萃取探针的涂层材料。衍生多孔碳材料因种类丰富、可设计性强被广泛研究,研究主要集中在对衍生多孔碳材料的结构优化方面。但是衍生多孔碳材料在固相微萃取中的应用还存在如下问题:(1)共价有机框架衍生多孔碳材料的制备已取得较大进展,但将其应用于固相微萃取领域的研究仍较少;(2)有待进一步明确制备出的衍生多孔碳材料用作固相微萃取涂层表现出优异提取能力的机理;(3)有待进一步深入研究将衍生多孔碳材料用作固相微萃取涂层以实现对不同物理化学性质污染物的广谱高灵敏度分析。文章综述了近3年衍生多孔碳材料在固相微萃取中的应用研究,并展望了未来衍生多孔碳材料在固相微萃取中的研究前景。引用文献共56篇,主要来源于Elsevier。     

Multimodal Zr-Silicalite-1 zeolite nanocrystal aggregates with interconnected hierarchically micro-meso-macroporous architecture and enhanced mass transport property

Hierarchical porous architecture with interconnected trimodal micro-meso-macroporous systems constructed from uniform zeolite Zr-doped silicalite-1 nanocrystals has been prepared. The synthesis has been made by using glycerin as a reaction medium via a quasi-solid-state crystallization of hierarchically meso-macroporous zirconosilicate precursor under the effect of the structure directing agent TPAOH. The presence of glycerin is crucial in the synthesis systems to maintain the porous hierarchy. The pores inter-connectivity, Zr location in the framework, the acidity and the catalytic activity have been studied by laser-hyperpolarized (129)Xe NMR spectroscopy, UV-visible spectroscopy, temperature-programmed desorption of ammonia and the catalytic isopropylbenzene cracking probe reaction, respectively. The products possess well-defined macrochannels interconnected with mesopores located in the macropore walls, which in turn have been constructed from microporous MFI-type zeolite units. (129)Xe NMR study indicated that the hierarchically micro-, meso-, macro-pore systems are homogeneously distributed throughout the final materials and well interconnected, which is important for molecular diffusion. The TPD-NH(3) investigation revealed that the hierarchically micro-meso-macroporous materials constructed from zeolite Zr-Silicalite-1 nanocrystals present strong acidity.     

Synthesis of functional hybrid silica scaffolds with controllable hierarchical porosity by dynamic templating

We report a facile one-pot synthesis of hierarchically porous scaffolds, with independent control over nanoparticle mesoporosity and scaffold macroporosity. Our technique combines the chemistry of mesoporous silica nanoparticles with the control afforded by dynamic templating of surfactant mesophases. These materials are readily functionalizable and allow controllable spatial variation in macroporosity.     

Heteroleptic metal alkoxide "oxoclusters" as molecular models for the sol-gel synthesis of perovskite nanoparticles for bio-imaging applications

Systematic structural study of the molecules, resulting from microhydrolysis of heterometallic beta-diketonate alkoxides of barium and strontium (single-source precursors of perovskite oxide materials), demonstrates that the structures of these products result from a thermodynamically driven self-assembly of metal cations and ligands directed towards the most densely packed cores. The ratio between metal cations, and of the cations to bidentate heteroligands, is easily changed to enable the highest packing density. The key to the application of single-source precursors appears to be the use of stoichiometric or superstoichiometric water amounts together with solvents preventing diffusion of possible homometallic intermediates. Eu-doped BaTiO3 nanoparticles have been successfully obtained and characterized.     

Synthesis and physico‐chemical studies of double alkoxides and their allied compounds

Alkoxide‐based molecular routes used as single‐source precursors for the synthesis of ultrafine materials with correct stoichiometry ratios have become an area of intense scientific interest due to the technological relevance in terms of simple equipment, low‐temperature processing and low cost. The crystallization behavior of allied compounds can be controlled with the help of tuning the properties of different chelating agents in the reaction conditions to increase the solubility of metal alkoxides. Physico‐chemical studies of alkoxides and their derivatives were carried out using FTIR, NMR, mass spectrometry, thermogravimetric analysis (TGA)–differential thermal analysis (DTA) and scanning electron microscopy (SEM). The mass spectra show the same types of fragmentation pattern in the compounds. The X‐ray diffraction patterns show enhanced homogeneity. TGA–DTA measurements show that thermal decomposition occurs in steps and depends entirely on the chemical composition and the synthesis route. The SEM observations reveal a high microstructural uniformity of polycrystalline nature. Copyright © 2005 John Wiley & Sons, Ltd.     

Sol-Gel Derived Polysiloxane-Oxide Hybrid Materials: Extent of Phase Interaction

Polymethylsiloxane-oxide hybrid materials can be easily prepared by co-hydrolysis of diethoxydimethylsilane, (DEDMS) and methyltriethoxysilane (MTES) and Ti, Zr and Al alkoxides. The molar ratio between precursors and the nature of metal alkoxides strongly influence the chemical reactions in solution and thus the chemical homogeneity of the gel network. This aspect depends on the degree of co-condensation obtained by the formation of oxygen bridged heterometallic bonds, and affects the structure and properties of polysiloxane-oxide materials.This paper presents the recent results obtained on polymethylsiloxane-oxide materials by equilibrium swelling experiments, dynamic mechanical thermal analysis (DMTA) and mechanical properties measurements. The results highlight the influence of nature and load of the metal oxide precursor on the extent of phase interaction in the hybrid gels. The ability to promote the silanol condensation in DEDMS-derived gels is pointed out by the determination of the soluble fraction of the hybrids and the average molecular weight of the polydimethylsiloxane chains.     

New families of supermicroporous metal oxides: the link between zeolites and mesoporous materials

Sol-gel hydrolysis reactions in propanol of two or more metal acetates or alkoxides in n-alkylamines have been found to yield porous mixed oxides with the presence of pores largely in the 10-20 A region.     

Hierarchically porous carbon cages synthesized through in situ migration of templates

Hierarchically porous networks have been fabricated through immigration of templates.